Crystal structure and conduction property of the first quasi-one-dimensional conductor of tetrathiafulvalenium salt with mixed inorganic anions, (TTF)(ClO4)0.14±0.02(Cl)0.42±0.08

Preparation, structure and conduction properties of SeCN-containing mixed anion TTF conductors

“…The first mixed anion TTF conductors was found during an attempted electrochemical preparation of a complex between TTF and Ni(dmbit) 2 (dmbit~dimercaptobenzoisotrithione{) in 1,2-dichloroethane with tetrabutylammonium perchlorate as the electrolyte. 12 This electrolysis yielded long needle-like crystals which were found to be (TTF)(ClO 4 ) 0.14 (Cl) 0.42 . A chloride ion that appeared seems to have derived from the 1,2-dichloroethane employed as the solvent.…”

“…The Se and N atoms in the SeCN anion could not be found in the analysis, most probably due to its orientational disorder. The occupancy factors were adjusted so that those of chloride (Cl(1) and Cl(2)) and carbon (C (11) and C (12)) are in accordance with the composition determined by the elemental analysis. Furthermore, the occupancy ratios between Cl(1) and Cl (2), and between C(11) and C (12), were refined by the least squares method.…”

“…In the temperature dependence of (TTF)(Cl) 0.42 (ClO 4 ) 0.14 , the VRH conduction is clearly evidenced. 12 There is only one exception among them which does not follow the VRH model: (TTF)(SCN) 0.47 (NO 3 ) 0.10 , which follows Arrhenius conduction and in which anions are partially ordered in their lattice due to its nearly commensurate composition. 15 When the SeCN ion is introduced as the mixed anion pair, the conductivity of the salt drops by another order of magnitude, as shown in Table 1.…”

“…The crystal structure was analyzed for the seven of the currently identified 21 mixed anion TTF conductors. They were (TTF)(Cl) 0.42 (ClO 4 ) 0.14 , 12 (TTF)(Cl) 0.60 (BF 4 ) 0.02 , 13 (TTF)(Cl) 0.66 (SCN) 0.09 , 13 (TTF)(Cl) 0.28 (NO 3 ) 0.59 , 16 (TTF)(SC-N) 0.47 (NO 3 ) 0.10 , 15 (TTF)(SCN) 0.12 (Cl) 0.57 , and (TTF)(Se-CN) 0.26 (Cl) 0.43 . All of them have a tetragonal lattice and space group P4 2 /mnm and are isostructural to each other except (TTF)(Cl) 0.28 (NO 3 ) 0.59 , which has an orthorhombic lattice and space group Pnnm.…”

Effect of Anion Disorder on the Peierls Transition in the Commensurate One-Dimensional Conductors (TTF)(SCN)0.56(ClO4)0.01, (TTF)(NO3)0.59(Cl)0.28, and (TTF)(SCN)0.09(Br)0.59

“…Another effect is also anticipated in the condensation of the Peierls instability , which is inherent to an equally spaced quasi-1D chain. Recently, it has been shown that TTF salts with mixed anions form a new series of 1D conductors which are inherently disordered in the anion lattice because of its anion mixing. , When the 1D conducting chain is under the influence of random potentials, the electron−phonone coupling in the chain is smeared out, reducing to an incomplete structural change as was exemplified by the following new TTF conductors.…”